Methods for protecting the skin against actinic radiations



United States Patent METHODS FOR PROTECTING THE SKIN AGAINST ACTINIC RADIATIONS Albert F. Strobe], Delmar, and Sigmund C. Cafino, Castleton, N.Y., and Marvin R. Leibowitz, Edison, NJ assignors to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed May 29, 1962, Ser. No. 198,448

10 Claims. (Cl. 167-90) This invention relates to new and useful compositions and in particular to those compositions which are applied to the human skin, as for example, cosmetics, shaving lotions and creams, suntan lotions and the like which are characterized as having superior resistance to degradation and deterioration when exposed to actinic radiation such as sunlight, and which in addition aiford outstanding protection to the skin against the effects of sunlight including sunburning, wrinkling, and aging due to the actinic radiations.

The compounds which are herein contemplated have the following general formula:

R R and R =H, alkyl, aryl, substituted alkyl, etc.,

Ar represents an aromatic carbocyclic nucleus or a heterocyclic nucleus having aromaticity, i.e., at least one pair of conjugated double bonds.

Suitable R, R R and R suhstituents include the following: alky1-- methyl ethyl n-propyl iso-propyl n-butyl iso-butyl tertiary-butyl secondary-butyl n-amyl iso-amyl tertiary-amyl and the other isomeric amyls n-hexyl iso-hexyl and the other isomeric hexyls n-heptyl iso-heptyl and the other isomeric heptyls n-primary nonyl (nonyl-1) i nonyl- (2 nonyl- 3 nonyl- (5 Z-methyl-octyl-Z 4-ethyl-hepty1-4 2-methyl-4-ethyl-hexyl4 n-primaryl octyl, octyl-(Z) (capryl) 2-methyl-3-ethyl-pentyl-3 2,2,4-trimethy1-pentyl-4 2-ethyl-hexyl-1 2-methyl-heptyl-2 3-methyl-heptyl-3 4-methyl-l1eptyl-4 n-pr-imary decyl (decyl-1) decyl-4 (secondary decyl) 2-ethyl-octyl-3 (tertiary decyl) i 4-propylheptyl-4 (tertiary de'cyl) undecyl-l (n-primary decyl) undecyl-2 (n-secondary decyl) dodecyl-l (n-dodecyl) f tridecyl-l (n-tridecyl) tridecyl-7 3-ethyl-undecyl tetradecyl-I (n tetradec yl) pentadecyl-l (n-pentadecyl) pentadecyl-S hexadecyl (cotyl) heptadecyl-9 octadecyl-l 2-methy1 heptadecyl-2 eicosyl-l docosyl-l tricosyl-12 tetracosyl tricapryl pentacosyl hexacosyl heptacosyl octacosyl nonacosyl myricyl (30 carbons) alkenyl allyl (CH =CHCH methallyl (CH =C(CH CH crotyl (CH CH=CHCHCH pentenyl-l 'y-isopropyl allyl fi-ethyl-v-propyl allyl 2-methyl-octenyl-6 decenyl-l decenyl-Z undecenyl dodecenyl-2 octadecenyl docosenyl pentamethyl eicosenyl substituted alkylcy-ano-n-propyl cyano-isopropyl cyano-isobutyl cyano-n-amyl cyano-isoamyl cyanohexyl cyanoheptyl cyano-n-octyl cyano-nonyl cyanodecyl cyanol-auryl cyanosteary-l and the like hydroxyethyl hydroxy-n-propyl hydroxy-isopropyl hydroxy-n buty-l hydroxy-isobutyl hydroxy-n-amyl hydroxy-isoam-yl T hydroxy-hexyl hydroxy-heptyl hydroxy-nonyl hydroxy-decyl hydroxy-lauryl hydroxy-stearyl, and the like carbomethoxyet-hyl 1,2,3-oxathiazo1e pyn'dazine pyri idine pyrazine 1,3,5-triazine and fused ring systems of benzene with the aforementioned heterocyclics, e.g.,

benzothiophene benzofurane quinoline phthalazine benzimidazole 1,2,3 -benztriazole benzoxazole The aryl and hetero nuclei described above may also contain any of the alkyl, substituted alkyl, aryl and substituted aryl radicals mentioned as suitable of the various R substituents, and also may contain:

halogen acyl sulfonyl carboxamido oxy, etc., substituents which may vary the ultra-violet absorption spectrum but which do not affect the function, utility and stability of the compounds. Specific examples of such substituents are:

l-chlorobenzoyl 2-cblorobenzoy1 p-chlorophenyl sulfonyl o-tolyl sulfonyl p-chlorobenzoyl p-tolyl sulfonyl o-methylsulfonylbenzoyl hydroxy p-methylsufonylbenzoyl methoxy o-hydroxyethylbenzoyl ethoxy p-hydroxyethylbenzoyl ,carboxamido 2,4 dichlorobenzoyl N-methylcarboxamide 2,5 -dichlorobenzoy1 N-ethylcarboxamide 2,6-dichlorobenzoyl N,N-diethylcarboxamide 3-chloro-2-bromobenzoyl N,N-dimethylcarboxamide 4-chloro-2-brornobenzoy1 and the like.

In addition to compounds of Formula I, when Y=COX, the compounds may be doublets of the general formula: 7

wherein A=-O or NR and wherein n=1 or 2; when n=1 we have compounds of Formula I; when n=2 and R is as in Formula I. W is a bivalent bridging radical. Suitable W radicals include:

7 a It is of course clear that other non-chromophoric substituents may be present in the above radicals, e.g.,

CI-IC1CHC1 CHB1CH CHBr- I CHgCHzOH and the like.

In addition to theabove contemplated derivatives, polyoxyalkylated derivatives thereof arewithin the purviewof this invention. Any of the aforementioned derivatives containing at least one reactive hydrogen atom may be reacted with an alkylene oxide or a compound functioning as an oxide such as ethylene oxide,

propylene oxide, butylene oxide, butylene dioxide, cyclo-r hexane oxide, glycidol, epichlorohydrin, butadiene diox-,

ide, isobutylene oxide, styrene oxide and mixtures there- 1 of, and the like to yield the corresponding polyoxyalkylated product. Such reactive compounds include CNCH CY wherein Y is as defined in Formula I.

The preferred keto compounds are ketones and as illustrative thereof are:

Z-methylbenzophenone 3-methylbenzophenone 4-methylbenzophenone Z-chlorobenzophcnone 3-chlorobenzophenone 4-chlorobenzophenone Z-bromobenzophenone B-bromobenzophenone 4-bromobenzophenone Z-iodobenzophenone S-iodobenzophenone t-iodobenzophenone l-fluorobenzophenone i-cyanobenzophenone )enzophenonecarboxylic' acid-(2) Jenzophenonecarboxylic acid-( 3) Jenzophenonecarboxylic acid-(4) Z-benzoylbenzoic acid methyl ester l-benzoylbenzoic acid ethyl ester Z-benzoylbenzoic acid amide Z-benzoylbenzoic acid monoethyl amide I-benzoylbenzoic acid methyl ester i-benzoylbenzoic acid ethyl ester l-benzoylbenzoic acid methyl ester l-benzoylbenzoic acid ethyl ester l-sulfonamidebenzophenone l-sulfonamidebenzophenone l-ethylbenzophenone '.,4-dimethylbenzophenone 1,5-dimethylbenzophenone ,4-dimet-hylbenzophenone l,4'-dimethylbenzophenone ,4'-dimethylbenzophenone ,4'-dimethylbenzophenone -propylbenzophenone -isopropylbenzophenone ,4,S-trimethylbenzophenone ,4,6-trimethylbenzophen-one ,4,2'-trimethylbenzophenone ,4,3'-trimethylbenzophenone -methyl-Sisopropylbeniophenone ,3,4,6-tetramethylbenzophenone ,3,5,6-tetramethylbenzophenone 8E 2,4,2,4'-tetramethylbenzophenone 2,5,2,5'-tetramethylbenzophenone 2,4,3, -tetramethylbenzophenone 2,4,6,3',5'-pentamethy1benzophenone 2,2'-dimethyl-5,5'-di-isopropylbenzophenone 4-n-octylbenzophenone 4-cyclobenzylbenzophenone 2-benzoylbenzophenone 4,4'-dicyclohexylbenzophenone 4,4'-di-p-toluy1benzophenone 2-phenylbenzophenone 3-phenylbenzophenone 4-phenylbenzophenone 2-propenylbenzophenone 2-allylbenzophenone N,N-dimethy1-2-sulfonamidebenzophenon 4-phenethylbenzophenone Z-carbox-aniidobenzophenone 2-hydroxybenzophenone 3-hydroxybenzophenone 4-hydroxybenzophenone Z-methoxybenzophenone 3-methoxybenzophenone 4-methoxybenzophenone 2-ethoxybenzophenone 3-ethoxybenzophenone 4-ethoxybenzophen one 2-phenoxybenzophenone 3-phenoxybenzophenone 4-phenoxybenzophenone 4-xylyloxybe nzophenone 4-(m-tolyloxy)benzophenone 4-(p-tolyloxy)benzophenone 4-isopentyloxybenzophenone Z-acetoxybenzophenone 3-acetoxybenzophenone 4-acetoxybenzophenone 4-cyclohexyloxybenzophenone, 4-benzy1oxybenzophenone 2,4'-difluorobenzophenone 4,4-difluorobenzophenone 2,4-dibromobenzophenone 2,6-dibromobenzophenone 2,4'-difluorobenzophenone: 2,2-dibromobenzophenone 2,4'- dibromobenzophenone 3,3'-dibromobenzophenone 4,4'-dibromobenzophenone 4,4'-dichlorobenzophenone 2,4-dichlorobenzophenone 2,4'-dichlorobenzophenone 3,4-dichlorobenzophenone 4,4'-di-iodobenzophenone 3,5-di-iodobenzophenone V 4-chloro-4-bromobenzophenone 2,2'-di-iodobenzophenone 2,4-dichloro-2,4-dibromobenzophenone 2,4,6-tribumobenzophenone 2,4,6-trichlorobenzophenone 2,5,2',5'-tetrachlorobenzophenone 2,4,2',4'-tetrachlorobenzophenoner 2-bromo-4'-phenylbenzophenone 2-ch1oro-4-phenylbenzophenone 2-bromo-2',4,4',6,6-pentamethylbenzophenone I 2-hydroxy-5-octylbenzophenone 4-chloro-3',4'-dimethylbenzophenone 1 -4chloro-3,4'-dimethylbenzophenone 2-chloro-2,4'-di-methylbenzophenone 2-bromo-4-rnethylbenzophenone 2-hydroxy-4-methylbenzophenone 4-hydroxy-2-methylbenzophenone 4-hydroxyethoxybenzophenone 3-hydroxy-4-methoxybenzophenone 2-hydroxy-4-methoxy-3-methylbenzophenone 4-methoxy-2-methylbenzophenone 4-methoxy-S-methylbenzophenone '11 3'-n-butyl-4'-n-propoxy-propiophenone 3'-methyl-4'-methoXy-butyrophenone 3'-methy1-4'-al1yloXy-butyrophenone 3-methyl 4-phenoxy+butyrophenone 3'-ethyl 4'-(p-chlorobenzyloxy)-butyrophenone 3' pentadecyl4'-methoxy-butyrophenone 4'-rnethoxy-3'-rnethyl-a-phenyl acetophenone 4'-butoxy-3'-methyl-butyrophenone 4'-isopentyloxy-3'-methyl-butyrophenone w-methoxy acetophenone w-ethoxy acetophenone w-eyclohexyloxy acetophenone w-phenoxy acetophenone v Z-phenacyloxy benzyl bromide Z-phenaeyloxy benzyl alcohol w-acetoxy acetophenone 4-chloro-w-hydroxy acetophenone 4-bromo-w-hydroxy acetophenone 4-bromo-w-acetoxy aoetophenone fl-isopropyl-acrylic acid (4-bromophenacyl ester) 4-ioclo-w-hydroxy acetophenone 4-iodo-phenacylcaprylate w-butyl mercapto-acetophenone. a-bromo-G-methylmercapto-S-methyl propiophenone a,;8-dibromo-6-acetoxy-3-methy1 butyrophenone a-acetoxy-2,5-dimethyl isobutyrophenone 2-hydroxyl -benzyl-propene- 1 Z-ethoxy-l-benzoyl-propene- 1 bis(3,5-dimethyl-4-propyl-3-pyrryl) ketone bis(-bromo-4-ethyl-3-rnethyl-2-pyrryl) ketone bis (3-ethyl-5-methyl-2-pyrryl) ketone bis(4-ethyl-3-methyl-2-pyrryl) ketone bis(5-ethyl-3-methyl-2'pyrryl) ketone bis(5-bromo-2-thienyl) ketone bis(5-methyl-2-thienyl) ketone bis(5 chloro-2-thieny1) ketone 5-chloro-2-thienyl-S-bromo-Z-thienyl ketone' (5-chl0ro-2-thienyl)-2-thienyl ketone S-methyl-Z-thienyl-S-brom0-2-thienyl ketone S-methyl-Z-thienyl-S-chloro-2-thienyl ketone 2,5-dimethyl-3-thienyl-5-chloro-2-thienyl ketone 5-chloro-Z-thienyI-S-ethyI-Z-thienyl ketone 2,5-dimethyl-3-thienyl-2-thienyl ketone bis(5-methyl-2-thienyl) ketone bis(2,5-dimethyl-3-thienyl) ketone 2-furyl-3-indolyl ketone 2-lfuryl-2-thienyl ketone Z-furyl ketone 3-thienyl ketone 2-fu1'yl-2-methyl-3-indolyl ketone 2-furyl-l-methyl-3-indoly1 ketone 3-indolyl-2-thienyl ketone 2-pyrryl-2-thienyl ketone 2,S-dimethyl-thienyl-2-thienyl ket one 2,5-dimethyl-3-thienyl-2-furyl ketone 2-pyridyl-4-pyridyl ketone 3-pyridyl-4-pyridyl ketone 5-chloro-2-thienyl-2-furyl ketone 5-chloro-2-thienyl-3-furyl ketone 3-indolyl-S-methyl-Z-thienyl ketone 3-indolyl-2-pyridyl ketone 2-thienyl-3-thienyl ketone 2-acetamido-4-phenyl-S-thiazolyl phenyl ketone 2-benzofuryl phenyl ketone Z-benzothiazolyl phenyl ketone S-bromo-Z-thienyl phenyl ketone 6-(benzyloxy)-3-methyl-2-benzofuryl phenyl ketone 5-bromo-2-benzofuryl-p-bromophenyl ketone 5,7-dibromo-2-benzofuryl phenyl ketone 4,5-dibr0mo-2-thienyl phenyl 'ketone 4,5-diiodo-2-pyrryl phenyl ketone V 4,5-diiodo-2-thienyl phenyl ketone 3,4-dimethoxyphenyl-2-furyl ketone 1,2-dimethyl-3-phenyl-3-pyrrolidyl phenyl ketone 3,5-dimethyl-4-isoxazolyl pentamethyl phenyl ketone 12 V 2,6-dimethyl-3-pyridyl phenyl ketone- 4,5-dimethyl-3-pyrryl phenyl ketone 4,5-dimethyl-2-thiazolyl phenyl ketone 2,5-dimethyl-3-thienyl phenyl ketone 5 2 5-dimethyl-3-thienyl p-tolyl ketone V 2,5-dimethyl-3-thienyl p-ethylphenyl ketone 2,3-dimenthyl-1-naphthyl-2-thienyl ketone 2,5-diphenyl-3-furyl phenyl ketone 4,5-diphenyl-3-isoxazolyl phenyl ketone 1,5-diphenyl-3-pyrryl phenyl ketone 2-furyl-o-tolyl ketone 2-furyl-p-tolyl ketone 5-iodo-2-thienylphenyl ketone 5-methyl-3-isoxazolyl phenyl ketone 15 2-methyl-3-indolyl phenyl ketone' 2-methyl-3-indolyl p-tolyl. ketone Z-methyl-1-naphthyl-2-thienyl ketone Z-methyl-S-benzoxazolyl phenyl ketone S-methyl-Z-thiazolyl phenyl ketone 5-methyl-3-phenyl-4-isoxazolyl phenyl ketone S-methyl-l-phenyl-1,2,3-triazol-4-yl phenyl ketone 2-methyl-3-pyridyl phenyl ketone l-naphthyl-Z-pyridyl ketone. l-naphthyl-4-pyridyl ketone l-naphthyl-3-pyridyl ketone 2-naphthyl-3-pyridyl ketone phenyl-5-phenyl-3-furyl ketone phenyl-5-phenyl-3-is0xazoly1 ketone phenyl-5-phenyl-3-pyrryl.ketone.

phenyl-S-phenyl-Z-pyrryl ketone phenyl-S-phenyl-2-thienyl ketone phenyl-4-thiazolyl ketone phenyl-5-thiazolyl ketone phenyl-Z-thienyl ketone phenyl-3-pyrazolyl ketone phenyl-2-pyridyl ketone The compositions of the present invention are applied to the skin in any dermatologically acceptable carrier.

40 The compounds employed hereinmay be appliedfrom aqueous systems in solution or in dispersed form. They may similarly be applied from oil systems and further, from oil and watersystems of both 'oil-in-water and waterin-oil emulson types.

The amount of compound to be used is not critical and may vary from as little as 0.01%

by weight based on the weight of the total composition to a composition wherein the compound or mixtures of compounds herein contemplated comprise the major amount of the composition, i.e., about up to 100%.

Since for most purposes it is not practical to employ the compounds per se (i.e., 100% active), the use in dermatological bases ispreferred. The following examples will serve to illustrate the present invention without being deemed limitative thereof.

otherwise indicated.

EXAMPLE 1 To the following hand lotion there is added 0.5 part of Parts are .by' weight unless fifi-diphenyl-a-cyanoacrylic acid isooctyl ester. .(protec- Triethanolamine Propylene glycol Polyvinyl pyrrolidone (K: 30)

Water Parts The protector is first added to, part A and then part A. is

. stirred into part B at C.,

EXAMPLE 2 An aerosol preparation of the formulation of Example l is made as follows: 92 parts formulation of Example 1 is charged with S-parts Generton 12/114 (57/43) in a conventional aerosol container. This composition is applied to the hand and affords similar protection as in Example 1.

EXAMPLE 3 0.2 part of the protector ofExample 1 is added to the following composition charged in an aerosol container:

Parts Polyvinyl pyrrolidone 0.5 Ethanol (85%) 70.0 Perfume 0.5 Propellant 12 30.0 Propellant 114 10.0

This composition makes an excellent after-shave lotion and when applied to the face, gives excellent protection against sunburn and the weathering effects of sunlight.

EXAMPLE 4 2 parts of the compound used in Example 1 (protector) dissolved in 98 parts mineral oil is an excellent oil base suntan lotion.

EXAMPLE 5 A condensation product of 15 moles of ethylene oxide with the hydroxyethyl ester of I3,B-diphenyl-a-cyanoacrylic acid is prepared as a 5% solution in water. This is applied tothe skin and affords excellent protection from actinic radiations.

EXAMPLE 6 The following compounds are added to mineral oil 100 parts) in the indicated amounts:

. Parts (a) u-Cyano-fi,,B-diphenyl acrylic acid ethyl ester 0.2

(b) u-Cyano-fi,/3diphenyl acrylic acid lauryl ester 0.2 (c) a-Cyano-,3,13-diphenyl acrylic acid methoxyethyl ester 0.5

(d) a-Cyano-p,/3-diphenyl acrylic acid tetrahydrofurfuryl ester 0.3 (e) a-Cyano-B,B-dipheny1 acrylic acid phenyl ester- 0.3 (f) u-Cyano-p,B-d-iphenyl acrylic acid tolyl ester 0.3 (g) a-Cyano-fl o-diphenyl acrylic acid anisyl ester 0.3

(h) e-Cyano-p,fi-bis(p hydroxyphenyl) acrylic acid ethyl ester 0.4 (i) a-Cyano-p-phenylp-4-chlorophenyl acrylic acid ethyl ester v 0.4 (i) a-Cyano-B,;8-diphenyl acrylamide 0.5 (k) u-Cyano-B-phenyl-B (3,4-dimethyl phenyl) acrylic acid ethyl ester 0.5 (l) a-Cyano-;3,,9-diphenyl-N,N-dimethyl acrylamide 0.5 (m) a-Cyano-B,5-diphenyl-arcylic pyrrolidide 0.5 (n) fLB-Diphenyl methylene malononitrile 0.4 (o) fi-Phenyl-p-thienyl methylene malononitrile 0. 6 .(p) ,B-Phenyl-B-furyl methylene malononitrile 0.6 (q) fi-Methyl-fl-thienyl methylene malononitrile 0.6 (r) B-Methyl-p-phenyl methylene malononitrile 0.6 (s) ;3,/3-Dithienyl methylene malononitrile 0.6

(x) a-Cyano-u-isooctyl-,B-phenyl acrylic acid ethyl ester (3) a-Cyano-pcyclohexyl-B-phenyl acrylic acid ethyl ester (z) a-Cyano-fi-propenyl-[S-phenyl acrylic acid ethyl ester EXAMPLE 7 A 2% aqueous solution of a-cyano Bphenyl-,8-(4-sulfophenyl) acrylic acid ethyl ester (solution slightly acid to a pH of 4 with acetic acid) is applied to the skin. The compound at this pH is substantive to the skin and dyes it whereby excellent protection is aiforded without resort to any film-former to bind or hold the product on the skin.

EXAMPLE '8 Example 7 is repeated using the following water dispersible, skin-substantive compounds:

The compounds of Examples 7 and 8 are incorporated into the following cream at a 2% concentration:

Parts Petrolatum 10 Mineral oil 5 Water 60 Glyceryl monostearate 7 Beeswax 3 Polyvinyl pyrrolidone |(K=30) 1 EXAMPLE '10 To the following face powder there is added 1% of the compounds of Examples 1 and 6:

Parts Titanium dioxide 5 Glyceryl monostearate 5 Allyl alcohol 3 Stear-ic acid 3 Liquid paraflin 3 Glycerin 4 Water 77 As pointed out above, mixtures of compounds may be used as well as single compounds. The former is indicated where a high degree of protection is desired over a wide band of radiation. In such cases it is desirable to blend two or more compounds having high K values in the far and near ultra-violet light, e.g., one having a K max. at 300 mp, one at 320 m and one at 340 m )For persons having a supersensitivity to ultra-violet light and particularly sunlight, such blends are preferred, and atford outstanding protection. For persons desiring a tanning action, a compound absorbing with a maximum at about 3110 to 330 lm/L would 'be indicated. Thus the compound of Example 1 will permit tanning while isooctyla-cyano- 3-phenyl-fi-thienyl acrylate will prevent tanning in concentrations of above about 5% in a suitable carrier. The compound of Example 6(0) will prevent tanning in even smaller concentrations, its K max. (in methanol) =79.4 at 354 mu.

1. In a method for protecting skin against actinic radi-.

ions, the improvement which comprises applying to the :in a composition comprising (I) a compound having theformula R 7 CN wherein (1) R is a radical selected from the group consisting of hydrogen, alkyl, aryl, alkenyl and hetero; (2) Y is selected from the group consisting of CN and wherein: X is selected from the group consisting of CR3 and /Rl N R R and R are independently any R radical; and

(3) Ar is a radical selected from the group consisting of aromatic carbocyclic nuclei and heterocyclic nuclei having at least one pair of, conjugated double bonds, and

(II) a dermatologically acceptable carrier; (III) said compound I being devoid of nitro groups and aromatic nuclear substituted amino groups.

16 2.1 In a method as defined in claim 1 wherein the com-v pound I is isooctyl-a-cyano-fi,fidiphenylacrylate;

3. A method as defined in claim ,1 wherein the carrier is water. 4. A method asdefined in claim 1 wherein the carrier is mineral oil.

5. A method as defined in claim 1 wherein the carrier is a water-in-oil emulsion.. I

6. A method as defined in claim l wherein the carrier is an oil-in-water emulsion.

7. A method as defined in claim 1 wherein the carrier is a fluorinated hydrocarbon propellant.

8.- A method as defined in claim 1 wherein Compound I is u-cyano-p-phenyl-g-(4-sulfophenyl)-acrylic acid ethyl ester.

I is ,S-phenyl-B-thienyl methylene malononitrile. v, 10. A method as defined in claim 1 wherein Compound I is isooctyl isocyano-fl-phenyl-B-thienyl acrylate.

References Cited by the, Examiner UNITED STATES PATENTS 2,853,423 9/1958 LaVia 16790 2,876,210 3/1959 Wynn 26049 3,052,636 9/1962 l Strobel 167-90 3,069,456 12/1962 Strobel 260 465 3,074,971 1/1963 Strobel 260-465 3,079,366 2/1963 Boyle 260-465 3,081,280 3/1963 Carlson 260465 l 3,085,097 4/1963 Strobel 260-'465 3,149,148 9/1964 Kladko 260- 465 FOREIGN PATENTS 216,501 8/1961 Austria.

IULIAN'S. LEVITT, Primary Examiner. A

A. P. FAGELSON, M. I. COHEN,Assistant Examiners.

9. Amethod asdefin'ed invclaim 1 wherein Compound 

1. IN A METHOD FOR PROTECTING SKIN AGAINST ACTINIC RADIATIONS, THE IMPROVEMENT WHICH COMPRISES APPLYING TO THE SKIN A COMPOSITION COMPRISING (I) A COMPOUND HAVING THE FORMULA AR-C(-R)=C(-Y)-CN WHEREIN (1) R IS A RADICAL SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, ALKYL, ARYL, ALKENYL AND HETERO; (2) Y IS SELECTED FROM THE GROUP CONSISTING OF CN AND -CO-X WHEREIN: X IS SELECTED FROM THE GROUP CONSISTING OF OR3 AND -N(-R1)-R2 R1, R2 AND R3 ARE INDEPENDENTLY ANY R RADICAL; AND (3) AR IS A RADICAL SELECTED FROM THE GROUP CONSISTNG OF AROMATIC CARBOCYCLIC NUCLEI AND HETEROCYCLIC NUCLEI HAVING AT LEAST ONE PAIR OF CONJUGATED DOUBLE BONDS, AND (II) A DERMATOLOGICALLY ACCEPTABLE CARRIER; (III) SAID COMPOUND I BEING DEVOID OF NITRO GROUPS AND AROMATIC NUCLEAR SUBSTITUTED AMINO GROUPS. 